Azidoethyl-thiophosphoric acid esters



Z,8Z9,l 1 1 ,l iat e nted Apr. 1, 1958 AZIDOETHYL-THIOPHOSPHORIC- ACID ESTERS Gerhard Schrader, Opladen, Germany, assignorto Far- 'benfabriken Bayer Aktiengesellschaft, Leverkusen,

Germany, a corporation of Germany No Drawing. Application January 23, 1957 Serial No. 635,589

Claims priority, application Germany February 9, 1956 one of them being sulphur, and R stands for alkyl radicals especially lower alkylradicals, such as methyl, ethyl, propyl, isopropyl, butyl, arn-yl, hexyl and the like. "Many thiophosphoric acid esters are well known as effective insecticides or more generally pesticides. Novel and effective compounds of this class of thioor dithiophosphoric acid esters now .have been prepared, which have outstanding properties with some respects especially they distinguish themselves by being effective against suckinginsects." V i It is known that ethylene-chlorohydrin may be reacted with the alkali metal salts of hydrazoic acid to give azidoethyl-alcohol in good yield. Furthermore, by the reaction of this alcohol with hydrobromic acid, azidoethyl-bromidemay easily be'preparedfrom azidoethyl-alcohol.

It has now been found that new compounds are ob-' tainable by esterification of azidoethyl-alcohol with O, O- dialkyl-thiophosphoric acid halides or by reaction of an azidoethyl halide, for instance the bromide, with the alkali metal or ammonium salts of O O-dialkylthiolor -thionothiol-phosphoric acids. 1 I 1 e These types of reaction may be represented by the fol- United States "Ofifice ing out this reaction. If thiolor dithio-phosphoric acid esters according to the above reaction scheme (b) have to be prepared also other salts than ammonium salts may be used for carrying out this reaction. These other salts may specially include alkali metal salts such as the sodium or potassium salt. The reaction according to scheme (b) may also be carried out using the free phosphoric acids and adding during the reaction a suitable I acid binding agent such as alkali metal hydroxides, carbonates, alcoholates and the like. Also tertiary amines may be used as acid binding agents. 1

In both cases the reaction generally is carried out'inan inert organic solvent. Examples of such inert solvents are water, lower alcohol or ketones 'such as methanol ethancl-, acetone-, methylethyl-ketones and the like. Sometimes it might be advisableto carry out the reaction in an excess of liquid, aliphatic, aromatic or heterocyclic p in wide limits, e. g, between about --20 to about 150 C. I

amines, thus using'tliese at the same time as acid binding agents. Especially in the above shown reaction (a) this method is preferred. The reaction temperature may vary But sometimes lower or'higher temperatures may also be advisable. A preferred temperature range is about 0C. to about 100 C.

These new phosphoric acid esters are suitable as plant protectives. As against comparable insecticides the new compounds distinguish themselves by'being highly eifective not only against sucking insects, but also against eating insects. Caterpillars and beetles may, for example, thus be controlled with the aid of the new agents. Moreover; the new compounds have a systemic action.

V The compounds of the presentinvention are generally valuable insecticides especially contact-insecticides and kill efiectively insects such as flies, aphids, mites and the like. Usually they are to be applied in the same manner as other well known phosphorous containing insecticides,

i. e. in concentrations from about 0.0001 to about 1% in dilutioniwith liquid or solid carriers. Examples of such liquid carriers are water, alcohols, liquid hydrocarbons, ketones and the like and as examples of solid carriers 7 there may be namedtalc, chalk,.bentonite, etc. Addilowing reaction schemes using 0, O-diethyl-thiophosphoric acid chloride and azidoethyl alcohol as reactants (a) or on the other side using azidoethyl bromide and Instead of the above described diethylesters, however, also the corresponding methyl, propyl, butyl and higher esters may be used according to this invention. In the reaction (11) instead of thiophosphoric acid chloride also other halides such as the bromide may be used for carrytional emulsifiers may be used, if necessary, and the new compounds may be dusted or sprayed, e. g. as aerosols or brought in contact otherwise withliving plants or msects. Y 'Q The following examples are given by way of illustrationonly without, however, limiting the present invention hereto:

Example 1 I/OC2H NLCHZ-CHL 0.1

44 grams of azidoethyl-alcohol are dissolved in 45 grams of anhydrous pyridine. 97 grams of diethylthionophosphoric acid monochloride are added with stirring at 10 C. and the mixture is stirred at room temperature for 12 hours. The reaction product is then introduced into a Example 2 s OCH:

Na-CH:.CH1.0.

52 grams of the ammonium salt of diethylthiolphos phoric acid are dissolved in 60 millilitres of anhydrous alcohol. 40 grams of 5-bromoazido-ethylalcohol are added with stirring at 55 C. and the temperature is maintained at 50-60 C. for an hour. The reaction product is filtered 0E with suction from the ammonium bromide separated out. The alcohol is then carefully removed by distillation. The residue thus obtained is taken up with 100 millilitres of benzene and washed three times with millilitre-portions of ice water. After separating the benzene layer, the product is dried and the solvent removed by distillation under vacuum. grams of the new azidothiolphosphon'c acid ester are thus obtained as a light yellow sparingly water-soluble oil.

Using 57 grams of the ammonium salt of diethyldithiophosphoric acid there is obtained by the same method as described before the fi-azidoethyl-0,0-diethyldithiophosphoric acid ester of the formula S OCiHb inan. amount of 33.5 grams as a yellowish oil, which is sparingly water-soluble. I

By the same method using the ammonium salts of the corresponding dimethylthiol-(or dithio)-phosphoric acids there are obtained the esters of the following formulae (H) 0 CH3 Ns.CHr.CH2.S.P

OCH;

4 Iclaim: 1. 0,0-dialkyl-(azidoalkyl)-thiophosphoric acid esters of the formula in which X and Y stand for a member selected from the group consisting of oxygen and sulphur, at least one of them being sulphur, and R stands for a lower alkyl radical. 2. 0,0-dialkyl-(azidoalkyl)-thiophosphoric acid esters of the formula in which R stands for a lower alkyl radical.

3. 0,0-dialkyl-(azidoalkyl)-thiophosphoric acid esters of the formula 0/0 E NLCH CIEILS-"l in which R stands for a lower alkyl radical.

4. 0,0-dialkyl-(azidoalkyl)-thiophosphoric acid esters of the formula in which R stands for a lower alkyl radical.

5. An azidoethyl-thiophosphoric acid ester of the formula S OCsHA NLCHLCHk-OJ? 001115 6. An azidoethyl-thiophosphoric acid ester of the formula ISI/OCHI NLCHLCHLOJ? OGHa 7. An azidoethyl-thiophosphoric acid ester of the formula fi/OOlHi N3.CH:.CH:.S.P

OCzHI 8. An azidoethyl-thiophosphoric acid ester of the formula fi/OClHS Na.CHt-CH1. .P

002 5 9. An azidoethyl-thiophosphoric acid ester of the formula 0 OCH:

NS.CH2.CHI.B.P

OCH:

No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,829,111 April 1,1958

Gerhard Schrader It is hereby oertified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 52 to 59, Formula (a) should appear as shown below instead of as in the patentlS OCaHa S OCaHs NR-CHZ-OHi-OH Cl1 N3.CH:.CE10-].])/

[SEAL] Attest: KARL H. AXLINE,

Attesting Ofiioer,

ROBERT C. WATSON,

Commissioner of Patents. 1 

1. O,O-DIALKYL-(AZIDOALKYL)-THIOPHOSPHORIC ACID ESTERS OF THE FORMULA 